Cellulosic compositions of matter containing organic ester amides



, Patented Aug. 19, 1941 CELLULOSIC COMPOSITIONs 0F MATIEB CONTAINING ORGANIC ESTER AMIDES JosephlLDiekeyand James G.McNaliy, i Roch ester No Drawing Application aim 26, ms, erial No. 204,373

9 Claims. (Cl. 106-183) V such as a compatible plasticizer, and a common solvent so: both, with or without other useful addition agents, so that the resulting products will have properties such as will make the com position highly advantageous forms in the plastic and analogous arts, such for instance, as the manufacture of wrapping sheets, phototoughness, and other properties which will enhance thevalue of the resulting product. Addi graphic film, artificial silk, varnishes or lacquers,

, lacquers and the like, and to produce a compo-' sition which will not injure, or be injured by, the substances or surfaces with which it is associated during manufacture. Other objects will become apparent to those skilled in the art to which this invention pertains.-

Whiie cellulose acetates, nitrates and have been known for decades it has also been known that to'utilize them in the various plastic rts it is necessary to mix therewith such plasticizing or conditioning agents as camphor,..castoi' oil, triphenylphosphate, monochlornaphthalene or the like. Certain ofthese and other addition agents are also added for the purpose of reducingthe inflammability of the product. Plastic inducing agents, such as the higher alcohols and their esters, ar sometimes also added. Similarly, addition compounds of various kinds "have been employed to increase flexibility, transparency,

ethers tion products for the same orsimilar purposes are also added to cellulose acetates, nitrates and ethers to prepare them for use in the other plastic arts, such as in the manufacture of lacquers, varnishes, artificial silk filaments, moulded com-. pounds and the like. While the plasticizers or other addition agents heretofore discovered have had their utility in the art, the increasing use to which cellulose derivatives have been put and the increasing number of desirable properties required of the cellulose derivativefor most purposes has made the discovery of new and, economical plasticizers or other addition agents a matter of considerable importance to the art.

We have discovered that valuable properties may be induced in and/or contributed to compositions containing cellulose derivatives such as cellulose acetate, by adding thereto as plasticizing compounds organic ester amides having the general formula:

whereinR is alkyl, cycloalkyl or aryl; R and R" are the same or different substituted, or unsubstituted alkyl, aryl or cycloalkyl groups: X .15 -CO; n is 1, b is 1 or more and B)! may stand for hydrogen. This class of compounds is com dicated above, be considered. ester amides, or

more specifically as N, N-di(acyloxyalk-yl) amides, are derived by reaction on allryol amines-of appropriate acids or anhydrides.

ESTER lAMIDES DERIVABLE FROM MONOE'IHANOLAMINE Compound Formula Boiling range Diaeetate Acetatc propionate ficetate propionate (isomer)-.

CHaC O-NH- 1p llgcetate butyrate cHaco-NH-mmococnn CHaCO-NH-CiHlOCOCH:

138-140 J2 mm. 162-l70 0.118 mm. 170-175 C./19 mm. 150-153" 0.] min. 170-175" 0.]19 mm.

ESIER AMIDES DERIVABLE FROM DIETHANOLAMINE Compound Formula Boiling range TI' CH3CONKC2H4OCOCHa)Z---- 212-214" 0.123 mm. T pmpinnnfe C2H5CO-N-(CzH4OCOCHah- 220-225 0.]23 mm. Acetate dlpropionate CH3CO-N-(C2H40COC2 5);- 215-220 C./26 mm. Diacetate butymw.-- CaH1CON-(CzH4OCOCHz)z 220225 0.121 mm. Tributyrate CaH7CO-N-(CzH4OCOCaH7): 205-2l0 C./ mm. Acetate dibutyrate. CHaC-O*N[C2H4OCOCaH1)2-- 220230 C./23 mm. Tributymte C:H CON(CzH4OCOCaH1)2 220-222 C./2 mm.

C3H4OCOC2HI Acetate propionate butyr'ate CHzC 0N I 240-260 0.]24 mm.

' CzH4OC0CaH7 CzH4OCOCaH7 Acetate butyrate caproate CHIC ON\ 232-240" 0.]20 mm.

' C H4OCOC5H 1 Examples of the preparation of typical compounds of this type are as follows:

PREPARATION or DIETHANOLAMINE DIACETATE PROPIONATE A mixture of 125 parts acetic anhydride and 80 parts propionic anhydride are added through a condenser,to 60 parts diethanolamine. The

reaction is extremely vigorous and a rate ofaddition is maintained so that the temperature remains at 100-110. When all the anhydrides have been added, the solution is refluxed gently for 30-60 minutes. The acids are then removed either at atmospheric pressure or under vacuum and the desired product distilled under diminished pressure. One hundred and fifty parts of are obtained, boiling at 21Q-220/23 mm.

PREPARATION OF ETHANOLAMIXE TBIACETATE PnErARA'rIoN on DIETHANOLAMINE TRICAPROATE One hundred and five parts of diethanolamine, 350 parts caproic acid, 5 parts concentrated sulfuric acid and 100'parts toluene are distilled in such a manner that the toluene is continuously separated from the water of reaction and returned to the reaction vessel. The distillation is stopped when 54 parts of water have been collected. The catalyst is then neutralized by washing with sodium carbonate solution and the product recovered by distillation. Three hundred and seventy-five parts of the tri-caproyl derivative are obtained, B. P. 235245/5 'mm.

PREPARATION or ETHANOLAMINE PROPIONATE BUTYRATE "acids formed in the reaction are distilled off and the ester-amide is distilled under reduced pressure. The compound is a colorless liquid an boils at 158'-161/11 mm. In accordance with the invention these compounds may be applied directly to the yarn during or after spinning, or may be added to the spinning solution itself. We have found that these compounds have exceptional solvent powers which enable them to dissolve mineral oils and blown and unblown, drying and semi-drying, vegetable and animal oils and accordingly they may be, and preferably are, employed as ingredients of yarn conditioning or lubricating 'formulas in conjunction with agents which function wholly or partially as lubricants.

In the following examples and description we have set forth several of the preferred embodiments of our invention, but they are included merely for purposes of illustration and not as a limitation thereof.

Erample 1 Parts Cellulose acetate C2H5OC2H4NH-C2HtOCOCH3 20 Triphenyl phosphate 20 Acetone 300 Ethyl acetate--. 100

p-Hydroxy ethyl (p or 7) hydroxy propyl amine dipropionate well known to those skilled in the art. A film so produced has permanently brilliant transparency and low inflammability, burning no moi:

readily than ordinary newsprint. Such fllm exceedingly tough and flexible, as shown by the fact that it will withstand many iolds upon "a modified schopper fold-tester (commonly used for such purposes) without breaking and that even after being subjected for a considerable number of days to air maintained at a temperature of 65 C. the film still maintains flexibility (in contrast to almost. complete lack of flexibilplasticizers may be compounded with other sin-,

gle or mixed organic esters of cellulose, such as cellulose aceto-stearate, aceto-malate, or cellu-, lose nitro-acetate, or with the cellulose ethe'rs, a

suitable solvent which will dissolve both the cellulosic derivative and :the plasticizer being employed.-

Inasmuch as our above described composition of matteris quite useful in the production of films and sheets it will be apparent that our new plasticizers may also be employed with advantage in, the other branches of the plastic art.

For example, as set forth in ourcopending application filed of even date herewith, compositions of matter similar to those described herein may be employed in the manufacture of artificial silk by the dry spinning method. With a proper coagulating bath they may be employed for wet spinning. It may be desired to employ a compo- Example- 2 Parts Cellulose acetate propionate 100v Butyl phthalate CHaCONH-C4HaOCOCHa Propylene chloride.. 200 Ethyl lac 100' Acetone 100 Example 3 Parts Cellulose nitrate 100 v cameo-om CH:C0-C:HlN-C1B'4N 0 0cm oo-cm V Ester gum 40 Ethyl acetate 200 Toluene 100 Etha 100 Example 4 Parts Cellulose butyrate ..l00

/CHr-CH| cn cn-N-coom 3 on. nkcm-cm oooom ,COCHl' Propylene chloride 300 Acetone 100 I Example 5 I 1 Parts Ethyl cellulose 100 ity where no plasticizer is used) demonstrating that the film will withstand ordinary usage satisfactorily for many years. The sum total of the above advantageous properties of a product produced from our new composition is considerably have previously been regarded as ticizers.

an order that those skilled in this my better understand our invention we would state, by way of illustration, that'for the manufacture of photographic film or other sheets our new composition oi matter may be compounded as iollows: 100 parts of acetone soluble cellulose acetate, i. e." cellulose acetate containing. from 38% to 42% acetyl radical, approximately, is dissolved with stirring at atmospheric temperature in 300 to 500 parts, preferably 400 parts, by weight, of

acetone. To this solution may be added from 5-50 parts by weight, of any one of the above plasticizers, it being found preferable to employ compounding lacquers.

sition of difierent viscosity or evaporation characteristics, but this is a mere matter of changing the solvent proportion or adding evapora-- tion retardants or other high or intermediate boiling constituents, as has been well known in the art for more than a decade.

Our novel plasticizers may be employed also with advantage in connection with a number of the known lacquer and varnish formulas with I which it may be found to be compatible. In such cases the plasticizer is usually first put into 'solu-- tion with the cellulose derivative solution and, i! non-solvents are added, only to such an extent as will not" precipitate the derivative iromsolution. Also the plasticizer is usually employed in larger amounts, such as from'iifl to 60 parts, in Other uses within the scope" of our invention will also suggest themselves to those skilled in the art and are to be ineluded within the scope'of the claims appended hereto.

"What we claim is:

group consisting of cellulose esters and ethers and5-50 parts of an amide selected from the group consisting of theorganic ester amides of I primary and secondary alkanol amines.

approximately .30 to 40 (parts thereof. The

amount of plasticizer may be decreased or increaseddepending upon whether itisdesired to tate plasticized .acetate.

6. Thin sheet wrapping material comprising- N-propionyl -betaessentially organic solvent soluble cellulose acetate plasticized with N-propionyl-beta-aminoethyl-propionate.

7. Thin sheet wrapping material comprising essentially@rganic solvent soluble cellulose acetate plasticized with mono-ethanol-amine-esteramide. v

9. Thin sheet wrapping material comprising essentially organic solvent soluble cellulose ester plasticized with mono ethanol amine ester amide.

' JOSEPH B. DICKE'Y. 

